EP0614239A2 - Pile secondaire non-aqueuse à dispositif de sécurité - Google Patents

Pile secondaire non-aqueuse à dispositif de sécurité Download PDF

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Publication number
EP0614239A2
EP0614239A2 EP94102970A EP94102970A EP0614239A2 EP 0614239 A2 EP0614239 A2 EP 0614239A2 EP 94102970 A EP94102970 A EP 94102970A EP 94102970 A EP94102970 A EP 94102970A EP 0614239 A2 EP0614239 A2 EP 0614239A2
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EP
European Patent Office
Prior art keywords
secondary cell
cell
electrochemical secondary
electrolyte
cathode
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP94102970A
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German (de)
English (en)
Other versions
EP0614239A3 (fr
Inventor
Pnina Dan
Jordan Geronov
Shalom Luski
Emil Megenitsky
Doron Aurbach
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Tadiran Batteries Ltd
Original Assignee
Tadiran Israel Electronics Industries Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from IL104903A external-priority patent/IL104903A0/xx
Application filed by Tadiran Israel Electronics Industries Ltd filed Critical Tadiran Israel Electronics Industries Ltd
Publication of EP0614239A2 publication Critical patent/EP0614239A2/fr
Publication of EP0614239A3 publication Critical patent/EP0614239A3/fr
Withdrawn legal-status Critical Current

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0566—Liquid materials
    • H01M10/0567—Liquid materials characterised by the additives
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
    • H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
    • H01M10/44—Methods for charging or discharging
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2200/00—Safety devices for primary or secondary batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M6/00—Primary cells; Manufacture thereof
    • H01M6/04—Cells with aqueous electrolyte
    • H01M6/06—Dry cells, i.e. cells wherein the electrolyte is rendered non-fluid
    • H01M6/10—Dry cells, i.e. cells wherein the electrolyte is rendered non-fluid with wound or folded electrodes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M6/00—Primary cells; Manufacture thereof
    • H01M6/14—Cells with non-aqueous electrolyte
    • H01M6/16—Cells with non-aqueous electrolyte with organic electrolyte
    • H01M6/162—Cells with non-aqueous electrolyte with organic electrolyte characterised by the electrolyte
    • H01M6/168—Cells with non-aqueous electrolyte with organic electrolyte characterised by the electrolyte by additives
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Definitions

  • This invention relates to rechargeable electrochemical cells and, more particularly, to an advantageous combination of anode, cathode and electrolyte within such a cell.
  • Rechargeable electrochemical cells typically include an anode, a cathode and an electrolyte.
  • the anode includes an alkali metal
  • the electrolyte is a solution containing an electrolytic salt which is usually an alkali metal as an anode
  • the cathode includes an electrochemically active material, such as compound of a transition metal.
  • the cell In the design of secondary cells two issues are of importance. On the one hand the cell must be safe; on the other hand the cell must have good performance, meaning that it must be able to produce energy and be capable of being cycled (charged and discharged) numerous times.
  • lithium As an anode material, the use of lithium as an anode material has been suggested. This is because it yields a cell having a very high energy density. That is, the cell that can store a substantial amount of electrical energy for a given size.
  • manganese dioxide (MnO2) and Li derivatives of manganese dioxide have been shown to be good cathode materials for such lithium-based cells as these materials provide a high electrochemical potential against lithium.
  • MnO2 is inexpensive, environmentally friendly and readily available. As a result, considerable effort has been devoted to development of secondary Li/MnO2 cells.
  • lithium-based cells Although some lithium-based cells have also met the requirement of being capable of being cycled numerous limes, they unfortunately have a number of problems in practical implementation. This is because these cells are not safe under abusive conditions such as overcharging, short circuiting or exposure to high temperature.
  • the basic problem with this type of secondary cell is the high reactivity of the lithium deposits, which are formed on the anode during cycling, with the electrolyte. Abusive operating conditions can increase the temperature within the cell to the point where the lithium increases the temperature and, consequently the pressure, within the cell.
  • venting This is a very hazardous condition and can lead to the splitting open of the cell, an event known as venting.
  • This venting can range from venting accompanied by a mild flame; through venting which is accompanied by vigorous flames; and to venting in which there is a violent explosion. All these venting conditions pose a considerable safety risk.
  • this invention provides for a secondary electrochemical cell comprising a Lithium based negative electrode; a positive electrode including the compound MnO2; and an electrolyte including an ionic salt and a solvent which is stable at temperatures below 100°C, but which polymerizes at temperatures greater than 100°C and at voltages higher than 4 Volts. This polymerization increases the internal resistivity of the cell and thereby decrease the flow of current and, simultaneously, the temperature within the cell.
  • the ionic salt is a Lithium salt and has concentration in the dioxolane solvent from 0.5 mole per liter of solvent up to the saturation point.
  • the salt is LiAsF6 at concentrations between 0.8M to 1.5M per liter.
  • the electrolyte is preferably a member of the dioxolane family and should include a stabilizer which acts as a polymerization inhibitor.
  • the electrolyte includes 1,3 dioxolane and the stabilizer is a member of the tertiary amine group and typically is one of the group consisting of: triethylamine, tributhylamine, tripropylamine, tribenzylamine, trioctylamine, triphenylamine, methylpiperidine.
  • Stabilizers such as triethylamine, tributylamine and triphenylamine, are preferably added at concentrations of between 50ppm (v/v) to 5 percent (v/v) while concentrations of 100 ppm (v/v) to 5000ppm (v/v) of triethylamine and tributylamine were found to be the most effective.
  • a cell of this type has been found to be particularly advantageous as it is a high density lithium based secondary cell which can be safely cycled many times and which is also appropriately safe under the abusive operating conditions of high temperature, overcharging and short circuiting.
  • the cap 14 is of standard industrial manufacture and includes an upstanding protrusion 30 which serves as the positive terminal of the cell.
  • the protrusion 30 is the top of a downwardly extending molybdenum pin 32 which is supported by a glass insulator 34.
  • the pin 32 is connected to the cathode 20 by way of a tab 36 and the anode 18 connected to the casing 12 by a tab 38.
  • a typical AA size cell of this type of construction would be 50mm long and have an outer diameter of 14 to 15mm.
  • the anode 18 and cathode 20 consist of 40mm wide strips respectively about 300mm and 250mm long. Typically the strip making up the anode 18 is 160 ⁇ m thick and that making up the cathode 20 is 250 ⁇ m thick.
  • the separator 24 is made of a porous strip about 700mm long, 48mm wide and about 25 ⁇ m thick.
  • the separator 24 is folded lengthwise over the cathode 20 and this combination together with the anode 18 is wound tightly to produce a roll 26.
  • the roll 26 is then covered in insulation and inserted into the casing 12.
  • the separator 24 is wider than the cathode, it protrudes beyond both the cathode and the anode and, in use, serves to prevent short circuiting between them.
  • the tabs 36, 38 are respectively connected to the pin 34 and casing 12, the remaining portion of the tab 36 insulated to prevent short circuit with the anode 18 and the cap 14 secured to the top of the casing.
  • Electrolyte 22 is then vacuum injected into the casing 12 through an aperture (not shown) in its base 16 which is thereafter sealed off.
  • the electrolyte which will be described in greater detail below, has a very low viscosity, it fills all the voids, including the pores in the separator and the cathode.
  • the anode 18 is typically a thin laminate foil consisting of a copper layer sandwiched between two lithium layers.
  • the copper layer is typically 20 ⁇ m thick and the lithium layers each 70 ⁇ m thick.
  • This type of lithium based anode is known in the art and can be obtained commercially. Furthermore, it is also possible to use a pure Lithium anode.
  • the cathode 20 preferably contains an active material which is manganese dioxide (MnO2) which may include lithium in one form or the other. Many different ways of producing this cathode active material are known.
  • MnO2 manganese dioxide
  • MnO2 active material For example, one way of producing an MnO2 active material is disclosed in United States Patent 4,133,856 (Ikeda, et al.). This patent teaches that gamma-phase manganese dioxide is heated for a period of at least 2 hours at a temperature of between 350° and 430°C so that the MnO2 is effectively dried and its structure changed from the gamma-phase to the beta-phase. This method is also referred to in U.S. Patent 5,279,972 (Moses).
  • the cathode active material can also include lithium, In which case it is preferable for the material to be lithiated manganese dioxide of the formula Li x MnO2.
  • This material is typically in granular/powder form which must be mixed with a conductive agent such carbon black or graphite in amounts of between 5% to 10% by weight, and with a commercial binder.
  • a conductive agent such carbon black or graphite in amounts of between 5% to 10% by weight
  • binders are known.
  • One type is an emulsion of Teflon® powder and water. This mixture can then be heated to make a putty which can be molded under heat and/or pressure.
  • the solvent is added in quantities of about 70% solvent to binder plus cathode material.
  • the solvent can, for example, be propanol, ethanol, isopropanol or one of the family of saturated olefins such as C10H22 (decane), C9H20 and C11H24.
  • the mixture is rolled onto an aluminum grid and baked at about 270°C for 1 to 4 hours.
  • the temperature and timing of this step is, to a large degree, a matter of choice but it is important that sufficient heat be applied so that the binder melts and binds with the active material, and that the solvent evaporates.
  • the aluminum grid acts both as a support for the cathode material and as a collector for electrons.
  • the electrolyte 22 is important to the safe operation of the cell. It should include a solvent which is stable and which, together with a suitable ionic salt forms a conductive solution at typical cell operating temperatures.
  • the solvent should, however, be such that it polymerizes in the cell so as described at unsafe temperatures, above about 100°C and at high voltages of above about 4V. These conditions would typically be reached when the cell is overcharged at high currents or short circuited. This polymerization is very effective in that it substantially increases the resistivity of the cell and thereby terminates its operation and precludes the possibility of further hazardous reactions between the Lithium and the electrolyte itself.
  • the electrolyte is constituted by a solution of a member of the dioxolane family and most preferably by 1,3-dioxolane, a lithium salt and a tertiary amine polymerization inhibitor (stabilizer).
  • concentration of the lithium salt in the dioxolane can vary from 0.5 mole per liter of dioxolane up to the saturation point.
  • the lithium salt of choice is lithium hexafluoroarsenate (LiAsF6) at concentrations between 0.8 to 1.5 moles per liter.
  • 1,3-dioxolane in conjunction with an MnO2 based cathode active material produces very good results.
  • 1,3-dioxolane with the LiAsF6 polymerizes at high voltages (above about 4.0V) and/or under high temperatures (above about 100°C).
  • the electrolyte in combination with the other components will be stable at normal operating temperatures and when the Voltage across the cell is within the operating voltage window of the cell.
  • the electrolyte, in combination with the other elements must polymerize when the conditions are beyond the normal operating parameters.
  • the performance of the electrolyte can be enhanced by the use of a stabilizer which inhibits the polymerization of the electrolyte at operating temperatures.
  • This stabilizer is typically one of the group of tertiary amines and preferably is one of the group consisting of: triethylamine, tributhylamine, tripropylamine, tribenzylamine, trioctylamine, triphenylamine, methylpiperidine. A concentration of 1000ppm of stabilizer has been found to yield satisfactory results.
  • the separator 24 functions to keep the cathode and anode apart to prevent short circuiting but is porous to allow the flow of ions across it.
  • Many different separator materials are available commercially, for example the polypropylene separator which is sold under the designation 3402 by Hoechst Celanese.
  • a number of AA size cells of the invention containing a Li metal anode; a Li x MnO2 cathode; an electrolyte of 1,3-dioxolane, 1 mole per liter LiAsF6 and 1000ppm v/v tributhylamine; and a polypropylene separator were used in this experiment.
  • Fig. 5 describes the behavior of the same type of cell as in Experiment 1 but this time exposed to overcharge conditions at a curtent of 1A. The cell had previously been cycled 50 times.
  • the charging voltage increased rapidly to more than 10V when the cell voltage reached 4.1V. This situation was reached after the cell was overcharged for 3 hours. Importantly, the temperature and the current (not shown) decreased at the same time the voltage increased. The cell was tested for a further 20 minutes and remained intact after this test.
  • Electrolyte A was a dioxolane/LiAsF6/1000 ppm tributhylamine solution and electrolyte B a prior art EC/PC/LiAsF6 solution.
  • Cells of both types were initially cycled at a charge rate of 60mA per hour and discharged at a rate of 250mA per hour. This type of cycling is typical of normal operating conditions. Thereafter the cell containing electrolyte A was charged at 250mA per hour (for about 2.5 hours per charging cycle) and discharged at the same rate. The cell containing electrolyte B was charged at the more advantageous rate of 120mA per hour (for about 5 hours per charging cycle) and also discharged at 250mA per hour. Both cells were cycled between 2.0 and 3.4V at these respective rates until they reached about 65% of their capacity.
  • cell A reached the end of its life, with 65% of the capacity it had after the second cycle, after 120 cycles.
  • cell B was cycled only 50 times before developing short circuits and failing as a result of formation of dendrite bridges in the electrolyte.
  • the cell of this invention can be treated to increase its life expectancy when it is to be exposed to conditions of rapid charging (such as the tested charging rate of 250mA per hour). This can be achieved by first cycling the cell at the usually recommended normal rate, of 60mA per hour charge and 250mA per hour discharge, for about two to ten times. The optimum number of these cycles has yet to be determined, but it is believed that they should be sufficient to allow lithium to redeposit on the anode.
  • the cell After this cycling, the cell can be rapidly charged as shown. Although this reduces its potential life from over 250 cycles to about 120 cycles, it is a substantial improvement over rapid charging without the initial slower charging steps (which would yield a life of less than 50 cycles even in the cell of this invention). It is furthermore anticipated that this method may also be applied to other secondary cells as well.
  • a cell identical to the one used in Experiment 1 was tested at high temperature.
  • the cell was placed inside an oven, in which a thermocouple was attached to the outer casing of the cell.
  • the oven was heated at rate of 3°C per minute. When the cell's can reached 128°C, it vented without noise, fire or any explosion.
  • the cell had previously been cycled 120 cycles at 250mA per hour discharge and 60mA per hour charge.
  • the secondary cell of the invention performs well under the adverse conditions of high and low temperature, short circuit and overcharging.
  • the cell is shown to be capable of being cycled many times.
  • the addition of the stabilizers gives the cell an added shelf life, even at temperatures of as high as 80°C.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Inorganic Chemistry (AREA)
  • Secondary Cells (AREA)
  • Battery Electrode And Active Subsutance (AREA)
EP94102970A 1993-03-01 1994-02-28 Pile secondaire non-aqueuse à dispositif de sécurité. Withdrawn EP0614239A3 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
IL10490393 1993-03-01
IL104903A IL104903A0 (en) 1993-03-01 1993-03-01 Safe high energy density electrochemical rechargeable cell
US08/205,037 US5506068A (en) 1993-03-01 1994-03-01 Non-aqueous safe secondary cell

Publications (2)

Publication Number Publication Date
EP0614239A2 true EP0614239A2 (fr) 1994-09-07
EP0614239A3 EP0614239A3 (fr) 1996-10-16

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Application Number Title Priority Date Filing Date
EP94102970A Withdrawn EP0614239A3 (fr) 1993-03-01 1994-02-28 Pile secondaire non-aqueuse à dispositif de sécurité.

Country Status (6)

Country Link
US (1) US5506068A (fr)
EP (1) EP0614239A3 (fr)
JP (1) JPH0778635A (fr)
DE (1) DE4406617A1 (fr)
FR (1) FR2702312B1 (fr)
GB (1) GB2275818B (fr)

Cited By (8)

* Cited by examiner, † Cited by third party
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EP0759641A1 (fr) * 1995-08-23 1997-02-26 Moli Energy (1990) Limited Additifs aromatiques polymérisables comme protection contre la surcharge dans les piles au lithium non-aqueuses rechargeables
EP0776058A2 (fr) * 1995-11-17 1997-05-28 Moli Energy (1990) Limited Monomères aromatiques agents de développement de gaz pour la protection de piles au lithium non-aqueuses contre la surcharge
WO1998026467A1 (fr) * 1996-12-09 1998-06-18 Valence Technology, Inc. Additif de stabilisation de cellule electrochimique
EP0878861A1 (fr) * 1997-05-16 1998-11-18 Moli Energy (1990) Limited Additives polymérisables pour sauvegarder des batteries non-aqueuses rechargeables au lithium après surcharge
EP0944126A1 (fr) * 1998-03-18 1999-09-22 Hitachi, Ltd. Pile secondaire au lithium, son électrolyte, et appareil électrique utilisant celle-ci
NL1013484C2 (nl) * 1999-11-04 2001-05-09 Tno Werkwijze voor het vervaardigen van een oplaadbare 3V Li-ion batterij.
EP1245053A1 (fr) * 1999-10-18 2002-10-02 Bar-Ilan University Electrolytes non aqueux de cellules electrochimiques rechargeables, a forte densite d'energie
CN100433443C (zh) * 2004-03-29 2008-11-12 三星Sdi株式会社 锂电池的电解液及其制备方法以及包含它的锂电池

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US5616429A (en) * 1995-05-24 1997-04-01 Wilson Greatbatch Ltd. alkali metal electrochemical cell exhibiting reduced voltage delay and method of manufacture
KR100499114B1 (ko) * 1997-08-21 2005-09-26 삼성전자주식회사 리튬2차 전지용 전해액 및 이를 채용한 리튬 2차전지
JPH11260349A (ja) 1998-03-05 1999-09-24 Fujitsu Ltd リチウム二次電池及びそれに用いる正極合剤
FR2777386B1 (fr) 1998-04-14 2000-05-12 Commissariat Energie Atomique Procede de preparation d'oxyde de metal de transition lithie ou surlithie, materiau actif d'electrode positive comprenant cet oxyde, et accumulateur
JP2002518796A (ja) 1998-06-08 2002-06-25 モルテック・コーポレーション 安全保護用多官能反応性モノマーを含む非水電気化学セル
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KR100330148B1 (ko) 1999-05-03 2002-03-28 김순택 리튬 이차 전지용 전해액
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US7645543B2 (en) 2002-10-15 2010-01-12 Polyplus Battery Company Active metal/aqueous electrochemical cells and systems
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US9368775B2 (en) 2004-02-06 2016-06-14 Polyplus Battery Company Protected lithium electrodes having porous ceramic separators, including an integrated structure of porous and dense Li ion conducting garnet solid electrolyte layers
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KR101287848B1 (ko) * 2005-08-09 2013-07-23 폴리플러스 배터리 컴퍼니 보호된 활성 금속 애노드를 위한 순응 씰 구조체
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US8048570B2 (en) * 2005-08-09 2011-11-01 Polyplus Battery Company Compliant seal structures for protected active metal anodes
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EP1961068B1 (fr) * 2005-12-14 2018-10-24 LG Chem, Ltd. Electrolyte non aqueux et accumulateur comprenant celui-ci
WO2007075867A2 (fr) 2005-12-19 2007-07-05 Polyplus Battery Company Electrolyte solide composite pour la protection d'anodes en metal actif
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JP5932220B2 (ja) * 2008-02-12 2016-06-08 スリーエム イノベイティブ プロパティズ カンパニー 高電圧用カソードのためのレドックスシャトル
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EP1245053A4 (fr) * 1999-10-18 2005-08-10 Univ Bar Ilan Electrolytes non aqueux de cellules electrochimiques rechargeables, a forte densite d'energie
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US5506068A (en) 1996-04-09
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GB9403881D0 (en) 1994-04-20
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DE4406617A1 (de) 1994-09-08
FR2702312B1 (fr) 2004-10-01

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